Barium cerate nanoparticles for use in solid oxide fuel cells
View Patent ↗A process for forming alkaline earth metal cerate nanoparticles comprises combining a stable cerium oxide aqueous colloidal dispersion with soluble alkaline earth metal salts while maintaining colloidal stability. The resulting alkaline earth metal salts may be calcined to form alkaline earth metal cerate particles having a perovskite structure.
1. A process, comprising:
(a) combining an aqueous dispersion of cerium-containing nanoparticles with a substantially equimolar amount of a soluble alkaline earth metal material relative to cerium, thereby forming an aqueous reaction mixture; and
(b) heating said reaction mixture to dryness, thereby forming a powder comprising cerium-containing nanoparticles and alkaline earth metal-containing particles.
2. The process according to claim 1 , wherein said alkaline earth metal material comprises an alkaline earth metal selected from the group consisting of barium and strontium.
3. The process according to claim 1 , wherein said cerium-containing nanoparticles have a particle size in the range of 1 to 50 nm.
4. The process according to claim 1 , wherein said cerium-containing nanoparticles are crystalline.
5. The process according to claim 4 , wherein said cerium-containing nanoparticles have a cubic fluorite crystal structure.
6. The process according to claim 1 , wherein said cerium-containing nanoparticles comprise one or more dopants selected from the group consisting of zirconium, yttrium, ytterbium, gadolinium, europium, and combinations thereof.
7. The process according to claim 1 , wherein said aqueous reaction mixture further comprises a source of zirconium ions.
8. The process according to claim 1 , wherein said aqueous dispersion of cerium-containing nanoparticles is formed from an aqueous reaction mixture comprising a source of cerium ions, a nanoparticle stabilizer, a source of hydroxide ions, and an oxidant, and adjusting the temperature of the reaction mixture into the range of about 0° C. to about 100° C., thereby forming the aqueous dispersion of cerium-containing nanoparticles.
9. The process according to claim 8 , wherein said nanoparticle stabilizer comprises an ether carboxylic acid of formula I,
R—O—(CH 2 CH 2 O) n CHR 1 CO 2 Y (I)
wherein:
R represents hydrogen or a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group;
R 1 represents hydrogen or an alkyl group;
Y represents H or a counterion; and
n is 0-5.
10. The process according to claim 8 , wherein the nanoparticle stabilizer is a carboxylic acid selected from the group consisting of methoxy acetic acid, 2-[2-(2-methoxyethoxy)ethoxy]acetic acid and 2-(2-methoxyethoxy)acetic acid.
11. The process according to claim 8 , wherein the oxidant is selected from the group consisting of alkali metal perchlorate, alkali metal chlorate, alkali metal hypochlorite, alkali metal persulfate, ammonium perchlorate, ammonium chlorate, ammonium hypochlorite, ammonium persulfate, ozone, and hydrogen peroxide.
12. The process according to claim 1 , further comprising a step of calcining said powder to form a second powder comprising an alkaline earth metal cerate.
13. The process according to claim 12 , wherein said alkaline earth metal cerate is characterized by a perovskite crystal structure.
14. The process according to claim 12 , wherein said step of calcining includes heating to a temperature in the range of about 500° C. and about 1100° C.
15. An alkaline earth metal cerate powder prepared according to the process of claim 12 , wherein the second powder has a grain size of less than 40 nm and the alkaline earth metal cerate comprises one or more dopants selected from the group consisting of zirconium, ytterbium, gadolinium, europium, and combinations thereof, and comprises no other dopants.
16. An alkaline earth metal cerate powder of claim 15 , wherein said alkaline earth metal is barium.
17. An alkaline earth metal cerate powder characterized by a perovskite structure and a grain size of less than 40 nm, wherein the alkaline earth metal cerate comprises one or more dopants selected from the group consisting of zirconium, ytterbium, gadolinium, europium, and combinations thereof, and comprises no other dopants.
18. An alkaline earth metal cerate powder of claim 17 , wherein said alkaline earth metal is barium.
19. A process, comprising:
(a) combining an aqueous dispersion of cerium-containing nanoparticles with a substantially equimolar amount of a soluble alkaline earth metal material relative to cerium, thereby forming an aqueous reaction mixture;
(b) heating said reaction mixture to dryness, thereby forming a first powder; and
(c) calcining the first powder to form a second powder comprising an alkaline earth metal cerate.
20. The process according to claim 19 , wherein said step of calcining includes heating to a temperature in the range of about 500° C. and about 1100° C.